Lithium disilicate glass-ceramics

ABSTRACT

This invention is directed to lithium disilicate (Li 2 Si 2 O 5 ) based glass-ceramics comprising silica, lithium oxide, alumina, potassium oxide and phosphorus pentoxide. The glass-ceramics are useful in the fabrication of single and multi-unit dental restorations (e.g. anterior bridges) made by heat pressing into refractory investment molds produced using lost wax techniques. The glass-ceramics have good pressability, i.e., the ability to be formed into dental articles by heat-pressing using commercially available equipment. In accordance with one embodiment directed to the process of making the glass-ceramics, the compositions herein are melted at about 1200 ° to about 1600 ° C., thereafter cast into steel molds in the shape of cylindrical blanks (pellets), or alternately, cooled to the crystallization temperature. The resulting glass blank are heat-treated to form glass-ceramic blanks via a one or two step heat-treatment cycle preferably in the temperature range of about 400 ° to about 1100 ° C. The resulting glass-ceramic pressable pellets and/or blanks of desired shapes, sizes and structures are later pressed into dental restorations. Alternatively, instead of forming into pressable pellets or blanks, the pulverized powder is used to form a dental restoration using the refractory die technique or platinum foil technique.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. application Ser. No. 09/640,941, filed Aug. 17, 2000, now U.S. Pat. No. 6,517,623, which is a continuation-in-part of U.S. application Ser. No. 09/458,919, filed Dec. 10, 1999, now U.S. Pat. No. 6,455,451, which claims priority to U.S. Provisional Application No. 60/153,916, filed Sep. 14, 1999, U.S. Provisional Application No. 60/122,558, filed Mar. 2, 1999, and U.S. Provisional Application No. 60/111,872, filed Dec. 11, 1998, all which are incorporated herein by reference.

FIELD OF INVENTION

This invention relates generally to glass-ceramics comprising lithium disilicate and more specifically to glass-ceramics for use in the manufacture of dental restorations and methods of manufacture thereof.

BACKGROUND OF THE INVENTION

The use of lithium disilicate glass-ceramics for use in dental restorations has been suggested in the prior art. U.S. Pat. No. 4,189,325 to Barret et al. is directed to a glass-ceramic comprising lithium disilicate for use in dental restorations. The glass-ceramic requires the presence of Nb₂O₅ and Pt as nucleation agents. Barrett et al. introduced dental restorations made from castable lithium disilicate glass-ceramics in the Li₂O—CaO—Al₂O₃—SiO₂ system nucleated by Pt and Nb₂O₅. According to Barret et al., dental restorations are made by casting a melt into an investment mold, and devitrifying thereafter.

U.S. Pat. No. 4,515,634 to Wu et al. is directed to a castable glass-ceramic composition wherein the glass is melted and cast into a shape and is crystallized after it has been shaped. Therefore, the crystallization process is performed by the technician making the restoration, not the manufacturer of the dental material. Wu set al. suggests one way to improve properties of castable lithium disilicate dental restorations within the same Li₂O—CaO—Al₂O₃—SiO₂ system as described by Barrett et al. is by utilization of P₂O₅ as a nucleating agent. Both Barrett et al. and Wu et al. describe castable compositions having CaO as an essential ingredient believed to improve chemical durability of the resulting glass-ceramics. Chemical durability is one of the major issues that the Wu and Barrett inventions fail to address. For example, total alkali leaching rates for materials presented in Wu's examples were four to five times higher than those for commercial dental porcelain.

Castable dental ceramics as described in Barret et al. and Wu et al. employ melting glass ingots supplied by a manufacturer and casting dental articles into a refractory investment mold. Following the casting process, the cast articles are devitrified (crystallized) by the required heat-treatment steps. This process is very similar to casting metals whereby a heat-treatment step follows the casting process to increase hardness and strength.

U.S. Pat. Nos. 5,507,981 and 5,702,514 to Petticrew teach lithium disilicate compositions for use in dental restorations, but the method described therein implies forming glass into the shape of a dental restoration at temperatures much higher than the melting temperature of lithium disilicate and heat-treating the dental restoration after forming to convert the glass into a glass-ceramic.

German Patent Application No. DE19647739 to Schweiger et al. is directed to lithium disilicate compositions for use in dental restorations. The glass-ceramic bodies or blanks used to press dental restorations are defined as “sinterable glass-ceramics” which are produced from the starting amorphous glass powder by simultaneous sintering and powder crystallizing, which process is also known as surface crystallization. The glass must be in powder form to be crystallized. Additionally, the lithium disilicate compositions therein require the presence of La₂O₃, MgO and ZnO.

Many of the lithium disilicate compositions in the prior art require casting of the glass into the desired shape and crystallizing thereafter. The glass must be formed into the finally desired shape and thereafter heat treated to crystallize into a lithium disilicate phase. This may result in structural and other problems, since the microstructure is not formed by the dental materials manufacturer, but by the technician fabricating the dental restoration. Overprocessing by a technician may change the microstructure of the material to something not preferred or desired by the dental materials manufacturer. Moreover, some of the prior art compositions require the forming of the glass-ceramics by surface crystallization, limiting the forming and compositional possibilities of the material.

It is desirable to provide a lithium disilicate glass-ceramic which is pressable or formable after the lithium disilicate is formed. It is beneficial to provide a lithium disilicate glass-ceramic for use in the fabrication of dental restorations wherein crystallization is carried out by the dental materials manufacturer in the most controlled manner. It is beneficial to provide translucent lithium disilicate glass-ceramics having high strength and good presssability.

SUMMARY OF THE INVENTION

This invention is directed to lithium disilicate (Li₂Si₂O₅) based glass-ceramics comprising silica, lithium oxide, alumina, potassium oxide and phosphorus pentoxide in addition to other components listed below. The glass-ceramics are useful in the fabrication of single and multi-unit dental restorations including but not limited to orthodontic appliances, bridges, space maintainers, tooth replacement appliances, splints, crowns, partial crowns, dentures, posts, teeth, jackets, inlays, onlays, facing, veneers, facets, implants, abutments, cylinders, and connectors made by a variety of techniques including heat pressing into refractory investment molds produced using lost wax techniques or building and sintering powder onto refractory dies such as in the refractory die/foil technique. The glass-ceramics have good pressability, i.e., the ability to be formed into dental articles by heat pressing, also known as hot pressing, or injection molding, using commercially available equipment and good formability, i.e., the ability to be applied in powder form to a dental model, i.e., on a refractory die, and heated to form a dental restoration.

In accordance with one embodiment directed to the process of making the glass-ceramics, the compositions herein are melted at about 1200° to about 1600° C. and preferably in the range of about 1300° to about 1400° C. for a period of time, preferably for about 4 hours and thereafter quenched (e.g., water quenched or roller quenched) or formed into shaped pieces.

The resulting glass is heat-treated to form a glass-ceramic via a one or two-step heat-treatment cycle preferably in the temperature range of about 400° to about 1100° C. This crystallization heat treatment may comprise a nucleation step and a crystal growth step. Depending on the composition, the first, nucleation step, may be carried out in the range of about 450° C. to about 700° C. and preferably in the range of about 500° C. to about 650° C. for about 0.5 to about 4 hours and the second, crystal growth step, may be carried out in the range of about 800° C. to about 1000° C. and preferably in the range of about 830° C. to about 930° C. for about 0.5 to about 48 hours. The most preferable heat treatment comprises about a one hour soak at about 645° C. and a subsequent four hour soak at about 850° C.

The resulting glass-ceramic shaped pieces are provided in a variety of pellets and/or blanks of desired shapes, sizes and structures that may be used for pressing cores or other frameworks or shapes for dental products or restorations or alternatively, used for machining into dental restorations or products. The blank or pellet may be subjected to viscous deformation at a temperature in the range of about 800° to about 1200° C., and more preferably in the range of about 850° to about 950° C., and most preferably at less than about 930° C., under vacuum and with the application of pressure of between about 2 to about 8 bar (0.2 to 0.8 MPa) and preferably no greater than about 6 bar (0.6 MPa) to obtain a dental restoration. Moreover, it is possible that the blanks may be machined to a dental restoration of desired geometry.

Alternatively, instead of forming into pressable pellets or blanks, the pulverized powder, with or without additives, is used to form a dental restoration using the refractory die technique or platinum foil technique.

BRIEF DESCRIPTION OF THE DRAWINGS

Features of the present invention are disclosed in the accompanying drawings, wherein:

FIG. 1 is perspective view of a plunger system in a pressing furnace for use in the fabrication of dental restorations in accordance with one embodiment of the invention;

FIG. 2 is a perspective view of a bar fabricated from a high strength structural ceramic for reinforcement of dental materials;

FIG. 3 is a perspective view of a ceramic structural insert inserted into a wax model;

FIG. 4 is a cross-sectional view of a dental restorative with a reinforcing insert therein;

FIG. 5 is a perspective view of a pressing operation using the glass-ceramic herein; and

FIG. 6 is the dental product formed from the pressing operation of FIG. 5.

DESCRIPTION OF THE INVENTION

As will be appreciated, the present invention provides glass-ceramic compositions comprising a glassy matrix and lithium disilicate (Li₂Si₂O₅). The glass-ceramics are useful for the fabrication of dental restorations. The compositions of the lithium disilicate glass-ceramics comprise inter alia, silica, lithium oxide, alumina, potassium oxide and phosphorus pentoxide in the ranges given in Table 1 below. The glass-ceramic compositions of the invention have a combination of properties useful for dental restorations. The glass-ceramics have good pressability, i.e., the ability to be formed into dental articles by heat pressing, also known as hot pressing, or injection molding, using commercially available equipment. The glass-ceramics also have good formability, i.e., the ability to be applied in powder form to a dental model and heated to form a dental restoration. The glass-ceramics may further be sintered to full density and machined into a dental restoration.

Pressable ceramics employ some form of hot-pressing or injection-molding of the glass-ceramic materials, which may be in the form of a variety of shapes and sizes, such as but not limited to cylindrical blanks, otherwise known as pellets, tubular, rectangular, square, polygonal and similar shapes. The pellets contain one or more crystalline phases and their morphology as well as volume fraction are not significantly altered in the course of pressing. One reason for this is that the pressing temperature is typically lower than the melting temperature of the crystalline phases. This is a major advantage because microstructure is formed in the controlled conditions by the manufacturer of the glass-ceramic materials, e.g., pellets. Following pressing, the resulting dental article does not require crystallization heat-treatment. Similarly, the powder glass-ceramics contain one or more crystalline phases and their morphology and volume fraction are not significantly altered in the course of sintering during the fabrication of a dental article.

The glass-ceramic shaped pieces can be formed by a number of processes: (1) Glass can be formed into shapes and thereafter crystallized. Prior to crystallization, the glass may be formed into shapes by a variety of processes, such as, but not limited to, casting the molten glass into molds or drawing glass rods from the glass melt and subsequently sectioning into rods or other shapes. Depending on the forming process, the shaped pieces, such as, pellets, are taken from the mold, and crystallized, or the rods that are drawn from the glass are thereafter crystallized. These pellets cannot be shaded by the addition of pigments. Nevertheless, color can be imparted to these glass-ceramic pellets by adding certain oxides such as, but not limited to, CeO₂, Tb₄O₇, MnO₂, V₂O₅, NiO₂, TiO₂, and combinations thereof during melting of the parent glass compositions. Alternatively, (2) glass can be crystallized in bulk and subsequently milled into powder. Pigments and other additives can be added to the powder. The powder is formed into a pellet and partially or fully sintered. Pigments, if added, create color centers that impart a certain color to a translucent body of the dental article pressed from the pellet. The mechanism of crystallization in the two processes described above is volume crystallization. Volume crystallization as described in process two above may be used to form glass-ceramic powder without forming into a pellet.

Alternatively, surface crystallization may be utilized to crystallize a portion of the glass into one or more crystal phases. This involves milling glass into powder. Pigments and other additives can be added to the powder. This glass powder (amorphous, not crystalline) is formed into a pellet. The glass pellet is sintered and crystallized in the same firing cycle. Not all glass-ceramic materials can be crystallized and sintered simultaneously. Only certain materials and compositions prone to surface crystallization can be processed this way. The glass-ceramics processed from glass powder via simultaneous sintering and crystallization are sometimes called “sintered” glass-ceramics. Another term that can be used is “sinterable” glass-ceramics.

The compositions herein are prepared by mixing, in the desired proportions, the oxides and/or compounds that decompose to form the oxides, followed by fusing the ingredients to obtain the compositions in Table 1. Convenient raw material include lithium carbonate, silica, alumina, carbonates of potassium, sodium and calcium, ammonium phosphate, tricalcium aluminate, aluminum phosphate or aluminum metaphosphate and if necessary, Ta₂O₅, CeO₂, Tb₄O₇, titanium dioxide, and zirconium dioxide.

TABLE 1 Oxide, wt % Range 1 Range 2 Range 3 Range 4 Range 5 Range 6 SiO₂ about 62 to about 85 about 64 to about 70 about 62-85 about 64-70 about 64 to about 70 about 62 to about 76 B₂O₃ 0 to about 4.9 0 to about 2.7 0 to about 4.9 0 to about 2.7 about 0.5 to about 3.0 0 to about 5 Al₂O₃ about 1.5 to about 10 about 1.5 to about 6.0 about 5.1-10 about 5.2-9.0 about 1.5 to about 6.0 about 1.5 to about 10 F 0 to about 1.5 0 to about 1.5 0 to about 1.5 0 to about 1.5 0 to about 1.5 0 to about 1.5 ZnO 0 to about 5 0 to about 2 0 to about 5 0 to about 2    — 0 to about 5 CaO 0 to about 7 0 to about 0.9 0 to about 7 0 to about 0.9 0 to about 0.9 0 to about 7 MgO 0 to about 2 0 to about 2 0 to about 2 0 to about 2    — 0 to about 2 BaO 0 to about 7 0 to about 7 0 to about 7 0 to about 7 0 to about 7 0 to about 7 SrO 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 Cs₂O 0 to about 5 0 to about 5 0 to about 5 0 to about 5 0 to about 5 0 to about 5 Li₂O about 8 to about 19 about 10 to about 15 about 8 to about 19 about 10 to about 15 10 to about 15 about 8 to about 19 K₂O about 2.5 to about 7 about 2.5 to about 5 0 to about 7 0 to about 5 about 2.2 to about 5 0 to about 7 Na₂O 0 to about 5 0 to about 3 0 to about 5 0 to about 3 about 0.5 to about 3 0 to about 5 TiO₂ 0 to about 2 0 to about 2 0 to about 2 0 to about 2 0 to about 2 0 to about 2 ZrO₂ 0 to about 3 0 to about 3 0 to about 3 0 to about 3 0 to about 3 0 to about 3 P₂O₅ about 0.5 to about 12 about 2 to about 7 about 0.5 to about 12 about 2 to about 7 about 2 to about 7 about 0.3 to about 7.0 SnO₂ 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 Sb₂O₃ 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 Y₂O₃ 0 to about 3 0 to about 3 0 to about 3 0 to about 3 0 to about 3 0 to about 3 CeO₂ 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 Eu₂O₃ 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 Tb₄O₇ 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 0 to about 1 Nb₂O₅ 0 to about 2 0 to about 2 0 to about 2 0 to about 2 0 to about 2 0 to about 2 Ta₂O₅ 0 to about 2 0 to about 2 0 to about 2 0 to about 2 0 to about 2 about 0.5 to about 8.0

For each of the compositions in Table 1, the molar ratio of (Na₂O+K₂O+CaO+SrO+BaO)/(Al₂O₃+ZnO) is about ≦1.3. The compositions in Table 1 are melted at about 1200° to about 1600° C. and preferably in the range of about 1300° to about 1400° C. for a period of time, preferably for about 4 hours and formed into shaped pieces by methods mentioned above, e.g., into the shape of a pellet (i.e., cylindrical blank) or blanks of other shapes.

The resulting glass pellets are annealed at temperatures in the range of 300° to about 600° C. for a time in the range of about 15 minutes to about 8 hours. Thereafter, the pellets are heat-treated to form glass-ceramic pellets using a one or a two-step heat-treatment cycle preferably in the temperature range of about 400° to about 1100° C. This crystallization heat-treatment may comprise a nucleation step and a crystal growth step. Depending on the composition, the first, nucleation step, may be carried out in the range of about 450° C. to about 700° C. and preferably in the range of about 500° C. to about 650° C. for about 0.5 to about 4 hours and the second, crystal growth step, may be carried out in the range of about 800° C. to about 1000° C. and preferably in the range of about 830° C. to about 930° C. for about 0.5 to about 48 hours. The most preferable heat treatment comprises about a one hour soak at about 645° C. and a subsequent four hour soak at about 850° C.

The glass-ceramics comprise lithium disilicate. The resulting glass-ceramic pellets can be used to make dental restorations as described in Example 1.

Alternatively, the compositions in Table 1 are melted at about 1200° to about 1600° C. and preferably in the range of about 1300° to about 1400° C. for a period of time, preferably for about 4 hours and thereafter quenched (e.g., water quenched or roller quenched), or alternatively, cooled to crystallization temperature. If the melt is cooled to the crystallization temperature, it may remain in the same furnace. The resulting glass is heat-treated to form glass-ceramics using a one or a two step heat-treatment cycle preferably in the temperature range of about 400° to about 1100° C. This crystallization heat-treatment may comprise a nucleation step and a crystal growth step. Depending on the composition, the first, nucleation step, may be carried out in the range of about 450° C. to about 700° C. and preferably in the range of about 500° C. to about 650° C. for about 0.5 to about 4 hours and the second, crystal growth step, may be carried out in the range of about 800° C. to about 1000° C. and preferably in the range of about 830° C. to about 930° C. for about 0.5 to about 48 hours. The most preferable heat treatment comprises about a one hour soak at about 645° C. and a subsequent four hour soak at about 850° C.

The glass-ceramics comprise lithium disilicate. The resulting glass-ceramics are then pulverized into powder sieved to −200 mesh to provide powder with average particle sizes of about 30 to about 40 microns. Pigments, fluorescing agents, opacifying agents, and the like may be added to the powder in a wide range in an amount between about 0 and about 6 wt % and preferably in the amount of between about 0 and about 5 wt % and most preferably in the amount of about 0% to about 3 wt %. Moreover, reinforcing agents may be added to the powder in an amount of from about 0 to about 30 vol % and more preferably in an amount of from about 0 to about 20 vol %. The reinforcing agents may include fibers, whiskers, and particulate fillers and may be fabricated of any known material, preferably a glass or ceramic material. The powders may be used in powder form to produce a dental material or may be used to form and fuse (sinter) pressable pellets and/or blanks of desired shapes, sizes and structures.

Sintering of the pellets or blanks is carried out at temperatures in the range of about 800° to about 1000° C., and preferably in the range of about 850° to about 950° C. Sintering imparts sufficient strength for handling of the pellets or blanks. These pellets and blanks may be used for pressing cores or other frameworks or shapes for dental products or restorations. The cores may be provided with one or more coatings. The coatings may be selected from a ceramic, a sintered ceramic, a glass-ceramic, a porcelain, a glass, a glaze, a composite and mixtures thereof. The coatings preferably have a firing temperature in the range of about 700° C. to about 900° C. and a coefficient of thermal expansion (measured from room temperature to its transition temperature) of within about ±2.0×10⁻⁶/° C. of the dental core (measured at the same temperature range). The blank or pellet may be subjected to viscous deformation at a temperature in the range of about 800° to about 1200° C., and more preferably in the range of about 850° to about 950° C., and most preferably at less than about 930° C., under vacuum and with the application of pressure of between about 2 to about 8 bar (0.2-0.8 MPa) and preferably no greater than about 6 bar (0.6 MPa) to obtain a dental restoration. Moreover, it is possible that the blanks may be machined to a dental restoration of desired geometry using commercially available milling equipment such as the Maho HGF 500 5 Axis CNC Milling Machine available from Fraunhofer Institut Produktionstechnologie, Germany. When powder is used to fabricate dental restorations, the powder is applied to the mold using refractory die techniques or the platinum foil technique.

In an alternative method herein, the compositions in Table 1 are melted at about 1200° to about 1600° C. and preferably in the range of about 1300° to about 1400° C. for a period of time, preferably for about 4 hours and thereafter water quenched or cast into steel molds.

The quenched glass is comminuted to a powder. Pigments, fluorescing agents, opacifying agents, and the like may be added to the powder in a wide range in an amount between about 0 and about 6 wt % and preferably in the amount of between about 0 and about 5 wt % and most preferably in the amount of about 0% to about 3 wt %. Moreover, reinforcing agents may be added to the powder in an amount of from about 0 to about 30 vol. % and more preferably in an amount of from about 0 to about 20 vol. %. The reinforcing agents may include fibers, whiskers, and particulate fillers and may be fabricated of any known material, preferably a ceramic material.

The powder is compacted into a pellet or starting blank. The blank is thereafter simultaneously sintered and crystallized. Heat treatment may be one or more cycles in the temperature range of about 400° to about 1100° C. The crystallization may comprise a nucleation step and a crystal growth step. Depending on the composition, the first, nucleation step, may be carried out in the range of about 450° C. to about 700° C. and preferably in the range of about 500° C. to about 650° C. for about 0.5 to about 4 hours and the second, crystal growth step, may be carried out in the range of about 800° C. to about 1000° C. and preferably in the range of about 830° C. to about 930° C. for about 0.5 to about 48 hours. The most preferable heat treatment comprises about a one hour soak at about 645° C. and a subsequent four hour soak at about 850° C.

The blank or pellet may be subjected to viscous deformation at a temperature in the range of about 800° to about 1200° C., and more preferably in the range of about 850° to about 950° C., and most preferably at less than about 930° C., under vacuum and with the application of pressure of about between about 2 to about 8 bar (0.2-0.8 MPa) and preferably no greater than 6 bar (0.6 MPa) to obtain a dental restoration. Moreover, it is possible that the blanks may be machined to a dental restoration of desired geometry.

To achieve the required combination of properties, namely sufficient strength, formability below 950° C., by heat-pressing using commercially available dental presses such as the Autopress® Plus available from Pentron Laboratory Technologies, LLC, Wallingford, Conn., translucency and chemical durability, the optimal chemical combinations and crystallization treatment of the present invention are necessary. The best properties are obtained when the lithium metasilicate (Li₂SiO₃) and silica phases are nearly absent, the volume fraction of Li₃PO₄ is less than about 5% and the volume fraction of lithium disilicate (Li₂Si₂O₅) is between about 35% and about 60%. High aspect ratio morphology of the lithium disilicate phase is important and is believed to enhance mechanical properties, i.e., strength and fracture toughness of the glass-ceramic.

Li₂O and SiO₂ are instrumental in crystallizing the required amount of the lithium disilicate phase in the compositions of the present invention. Additionally, BaO and Cs₂O stabilize the residual glass and boost the refractive index of the residual glass to match that of lithium disilicate. Al₂O₃ and to a lesser extent, B₂O₃, if less than 3%, yield chemically durable glass-ceramics that exhibit a sufficiently low solubility. Alkali (Na, K, Cs) and alkaline earth metal (Ca, Ba) oxides are required to lower processing temperatures of the glass-ceramic. However some of them affect chemical durability more than others. With respect to the following group of alkali metals and alkaline earth metals of potassium, calcium, sodium, and barium; potassium is associated with the smallest decrease in chemical durability of lithium containing glasses, with calcium being next, and sodium and barium affecting chemical durability the most. However, the best combination of properties is achieved when those oxides are used in combination to achieve the so-called “mixed alkali effect.” F lowers the viscosity of the glass-matrix and enhances formability at temperatures below about 950° C. Y₂O₃ in combination with Ce₂O₃, Eu₂O₃ and Tb₄O₇ modify the refractive index as well as impart fluorescence. Nb₂O₅ and Ta₂O₅ modify the refractive index as well as aid nucleation and chemical durability of the resulting glass-ceramics.

The following Table 2 illustrates examples of the compositions of the invention.

TABLE 2 Oxide, wt % Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 SiO₂ about 68.8 about 70.0 about 70.1 about 68.1 about 69.5 about 68.8 about 65  about 67.2 about 68.9 about 72   B₂O₃ about 1.2  about 1.0  — — about 1.3  about 1.3  about 1.0 about 1.2  about 0.9  about 2.0  Al₂O₃ about 4.8  about 4.9  about 5.2  about 4.7  about 4.8  about 4.8  about 5   about 4.7  about 4.7  about 4.5  F — — — — — — — — — — ZnO — — — — — — — — — — CaO about 0.9  about 0.5  about 2.2  about 2.0  about 2.0  about 1.0  about 1   about 1   about 0.5  0 MgO — — — — — BaO about 2.8  about 1.4  — — — about 2.8  about 2.7 about 2.7 about 1.4  about 2.0  SrO — — — — — — — — — — Cs₂O — — — — — — — — — — Li₂O about 14.4 about 14.7 about 14.7 about 14.3 about 14.6 about 14.4 about 15  about 14.1 about 14.3 about 13.0 K₂O about 2.5  about 2.5  about 4.6  about 4.4  about 4.5  about 2.2  about 2.2 about 2.2  about 2.0  about 2.0  Na₂O about 1.4  about 1.4  — — — about 1.5  about 1.4 about 1.4  about 1.3  — TiO₂ — — — — — — — — — — ZrO₂ — — — — — — — — — — P₂O₅ about 3.3  about 3.6  about 3.4  about 3.3  about 3.4  about 3.3  about 3.5 about 3.2  about 3.5  about 3.0  SnO₂ — — — — — — — — — — Sb₂O₃ — — — — — — — — — — Y₂O₃ — — — — — — — — — about 0.5  CeO₂ — — — about 0.4  — — about 0.4 about 0.4  about 0.3  about 0.6  Eu₂O₃ — — — — — — — — — about 0.6  Tb₄O₇ — — — about 0.8  — — about 0.9 — about 0.3  — Nb₂O₅ — — — — — — — — — — Ta₂O₅ — — — about 2.0  — — about 1.9 about 2.0  about 1.8  — Molar ratio of about about about about about about about about about about (Na₂O + 1.772 1.398 1.727 1.787 1.772 1.777 1.66 1.765 1.307 0.777 K₂O + CaO + SrO + BaO):(ZnO + Al₂O₃) Three-Point 420 ± 60 440 ± 60 440 ± 50 Flexural Strength per ISO 6872, MPa As-pressed 42 25   34   Opacity (relative opacity units) CTE (25° C.- 10.4 10.1-10.6 10.5 10.0 9.9 500° C.), 10⁻⁶/ ° C.⁻¹

The following examples illustrate the invention.

EXAMPLE 1

Glass-ceramic compositions of the present invention were utilized to make glass-ceramic pellets. Glasses of compositions given in Table 3 were batched from the corresponding mixtures of carbonates, oxides and monoammonium phosphate (such as shown in Table 4 below for Examples 6 and 8) and melted at 1300° C. for 4 hours in fused silica crucibles. A portion of the molten glass was cast into steel molds to form pellets and the rest was quenched into water. Cast ingots having the shape of nine cylindrical pellets (D=11 mm, H=16 mm) attached to rectangular stems were quickly transferred from the steel molds to the annealing furnace operating at 450° C. The ingots were annealed for approximately 30 minutes and furnace-cooled. The water-quenched glass was separated from the water and dried. For the glass compositions of Examples 6 and 8, a portion of the quenched glass was separated and milled as a glass and the rest of the glass was loaded into fused silica crucibles for crystallization heat treatment in bulk.

TABLE 3 Raw batch composition, wt % Ex 6 Ex 8 K₂CO₃ 2.532 2.484 Ta₂O5 0 1.580 Li₂CO₃ 27.845 27.320 H₃BO₃ 1.735 1.702 CaCO₃ 1.41 1.383 CeO₂ 0 0.304 Na₂CO₃ 1.939 1.902 SiO₂ 53.826 52.811 Al₂O₃ 3.729 3.659 BaCO₃ 2.783 2.731 NH₄H₂PO₄ 4.202 4.123

The compositions of Example 6 and 8 were used to fabricate glass-ceramic pellets using three alternative processes described earlier, namely (1) the parent glass was cast into the shape of cylindrical blanks (pellets) and the pellets were heat-treated to form glass-ceramic pellets referred to below as cast-crystallized pellets; (2) the parent glass was quenched, subjected to heat-treatment to crystallize it in bulk and the resulting glass-ceramic was pulverized into powder, the glass-ceramic powder was compacted into the shape of pellets which were sintered to full density under vacuum and referred to as sintered pellets; (3) the parent glass was quenched, milled into powder, the glass powder was compacted into the shape of pellets which were sintered with simultaneous crystallization to form glass-ceramic pellets referred to below as powder-crystallized pellets. Glass pellets and the quenched glass in processes (1) and (2), respectively, were heat treated using the same two-step volume crystallization cycle comprising heating in air at the rate of 10° C./min to 500° C., holding for 2 hours at this temperature, increasing the temperature at a rate of 10° C./minute to 850° C., and holding at this temperature for 4 hours. In process (3) powder-crystallized pellets were pressed from glass powder and sintered/crystallized in a dental furnace using a cycle comprising heating in vacuum at the rate of 20° C./minute to 900° C., no hold.

These three types of pellets were used to make rectangular bars (23×4×2 mm) and rods (23 mm length×3.2 mm diameter) for measuring flexural strength in a standard 3-pt bending fixture described in ISO 6872 specification. The process was the same as that used to make dental restorations. The specimens were pressed into the cavities of refractory investment molds formed by the conventional lost-wax technique using well-described heat-pressing methods (referred to as well as injection-molding of dental glass-ceramics). Heat-pressing was carried out under vacuum in an AutoPress® dental pressing furnace (Pentron Laboratory Technologies, LLC, Wallingford, Conn.). The pressing cycle comprised heating from about 700° C. to about 920° C. and holding at the latter temperature for about 20 minutes prior to applying pressure. Pressure of 0.55 MPa (5.5 bars) was applied for about 7 minutes through a mold plunger assembly schematically shown in FIG. 1. Results of the 3-pt flexure tests for glass-ceramic pellets fabricated by three alternative processes described above for glass-ceramic compositions of Examples 6 and 8 are summarized in the Table 4 below.

TABLE 4 Glass- Example 6 Example 8 Ceramic CAST- POWDER- CAST- POWDER- Composition CRYSTAL- CRYSTAL- CRYSTAL- CRYSTAL- Pellet type LIZED SINTERED LIZED LIZED SINTERED LIZED 3-pt Flexure 420 ± 60 290 ± 40 250 ± 30 440 ± 60 Strength per ISO 6872, MPa As-Pressed 370 ± 40 320 ± 20 260 ± 20 370 ± 30 270 ± 40 300 ± 20 Rod (D = ⅛″) 3-pt Flexure Strength, MPa

Comparing the strength values obtained for the various types of pellets, the cast-crystallized pellets exhibited the highest flexure strength compared to the other two types of pellets and were fabricated with the least number of processing steps involved. The noticeable decrease in strength for the sintered and powder-crystallized pellets was attributed to accumulation of processing flaws introduced during the extra processing steps, especially the vacuum sintering step required to produce these types of pellets. The cast crystallized pellets herein generally have a 3-point flexure strength exceeding about 350 MPa and preferrably equal to or greater than about 370.

Moreover, the closeness of refractive indices of the matrix glass (˜1.5) and that of the crystallized phase—lithium disilicate—(˜1.55) allows for the possibility of translucent glass-ceramics. Specifically in the present invention, the refractive index of the glass matrix is increased to match that of the lithium disilicate phase by adding small amounts of heavy ions such as, but not limited to, Sr, Y, Nb, Cs, Ba, Ta, Ce, Eu and Tb.

The following examples in Table 5 illustrate the effect of different additions on translucency, strength and reactivity with investment of the resulting glass-ceramics. The composition of Example 6 (Table 2) was selected as a control composition for the purposes of this study. This composition was modified by adding 0.13 mole % of CeO₂, or 0.06 mole % of Tb₄O₇, or 0.26 mole % of Ta₂O₅, or La₂O₃, or Y₂O₃; and combinations of the latter with CeO₂. Opacity was measured on the pressed disk using an optical densitometer. Reactivity with investment was evaluated qualitatively by visual inspection of disks and copings prior to and after sand-blasting of the reaction layer. Surfaces of the disks were inspected for pittings under low-magnification (8×) stereomicroscope. Compositions comprising combinations of Ta₂O₅, and CeO₂ were found to have the best combination of high translucency (low opacity) and low reactivity with the investment.

TABLE 5 Oxide, wt % Ex. 6* Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 8* Ex. 23 SiO₂ 68.8 68.12 68.5 68.2 67.5 67.8 67.9 68.0 67.2 67.5 B₂O₃ 1.3 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Al₂O₃ 4.8 4.7 4.8 4.7 4.7 4.7 4.7 4.7 4.7 4.7 CaO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 BaO 2.8 2.7 2.8 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Li₂O 14.4 14.3 14.3 14.3 14.1 14.2 14.2 14.2 14.1 14.1 K₂O 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 Na₂O 1.5 1.4 1.5 1.4 1.4 1.4 1.4 1.4 1.4 1.4 P₂O₅ 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.2 3.3 Y₂O₃ — 1.04 — — — — 1.04 — — — CeO₂ — — 0.39 — — — 0.39 0.39 0.39 0.39 Tb₄O₇ — — — 0.85 — — — 0.85 — — Ta₂O₅ — — — — 2.02 — — — 2.01 — La₂O₃ — — — — — 1.5 — — 1.49 Molar ratio of 1.777 1.765 1.777 1.765 1.765 1.765 1.765 1.765 1.765 1.765 (Na₂O + K₂O + CaO + SrO + BaO):(ZnO + Al₂O₃) 3-pt Flexure 420 ± 60 440 ± 60 Strength per ISO 6872, MPa As-Pressed Rod 370 ± 40 370 ± 30 3-pt Flexure Strength, MPa As-pressed 42 35 39 37 27 25 31 32 25 24 Opacity (relative opacity units) Reactivity with — Medium Lower Higher Medium Higher Lower Medium Lower The investment Highest material *Correspond to compositions in Table 2.

EXAMPLE 2

Pellets of the compositions of Examples 2, 6, 8 and 9 were used to press a variety of dental articles in the AutoPress® dental press (Jeneric/Pentron, Wallingford, Conn.) at pressing cycles carried out under vacuum and involving heating from 700° C. to 920° C. and holding the temperature for 20 minutes prior to initiation of the pressing cycle. Pressure of 0.5 MPa was applied for 7 minutes through a mold-plunger assembly schematically shown in FIG. 1. The plunger assembly used to press the pellets into dental restorations may be a system such as that set forth in copending commonly assigned U.S. Pat. No. 6,302,186, which is hereby incorporated by reference. Disks of compositions of examples 11 and 13 were pressed as described above and chemical solubility was measured according to ISO 6872 and found to be significantly lower than the acceptable limit of 100 μg/cm².

To further increase the strength of the dental restorations produced by an injection-molding method the cast-crystallized pellets of the composition of Example 8 were used to press frameworks for four-unit anterior bridges and three unit posterior bridges with pontics reinforced by structural elements made from yttria-stabilized tetragonal zirconia (YTZP) bars. FIG. 2 shows a YTZP bar 20 used for reinforcing dental products.

YTZP bars (length=70 mm, height=4 mm, width tapered from 2.5 mm to 3 mm) received from Friatec Aktiengesellschaft (Division Frialit-Degussit, Mannheim, Germany) were thinned down using 120 grit silicon carbide sand paper, cut into smaller sections with a high-speed hand-piece equipped with a diamond wheel and further shaped using white stone (made from alumina). Surprisingly this YTZP material was relatively easily cut by a diamond wheel and could be ground and shaped by conventional white stone made from alumina.

These four-unit anterior and three-unit posterior frameworks were waxed up on a stone model at which time the structural elements were inserted into the wax model of the framework as shown in FIG. 3. A reinforcing insert or bar 30 is placed on stone model 32 and wax 34 is built up around bar 30. These hand-made structural elements fabricated manually from the commercially available YTZP material in the shape of bars and using tools readily available in each dental lab were relatively easily integrated into the wax-ups of the bridges suggesting that pre-fabricated YTZP pontics (inserts) can be used with even greater ease and convenience.

FIG. 4 shows a YTZP reinforcing insert or bar 40 enclosed in a lithium disilicate framework 42 made in accordance herein. FIG. 5 shows the pressing of a four-unit framework with a YTZP reinforcing insert or bar 50 therein. A lithium disilicate pellet 52 manufacture in accordance herein is shown in pressing position. FIG. 6 shows the finished pressed lithium disilicate framework 52F made from pellet 52 from FIG. 5 for a four-unit anterior bridge with YTZP reinforcing bar 50 therein.

Some of the pressed frameworks were sectioned to evaluate the integrity of the interface between the lithium-disilicate glass-ceramic and the YTZP structural elements (inserts). Surprisingly it was as well found that lithium disilicate glass-ceramic material of this invention is not only compatible in thermal expansion to the YTZP material but wets and bonds very well to this YTZP material.

The remaining pressed frameworks were veneered with OPC® 3G™ Porcelain (Pentron Laboratory Technologies LLC, Wallingford, Conn.) compatible both with lithium-disilicate glass-ceramics of the present invention and YTZP material.

EXAMPLE 3

Three different powders of lithium disilicate glass-ceramics given in Table 6 below were used to make jacket crowns. One powder was formed from the composition of Example 24, a second powder was formed from fifty percent of the composition of Example 25 and fifty percent of the composition of Example 26, and a third powder was formed from the composition of Example 26. The powders were mixed with water to a thick paste consistency and were applied to refractory dies made form Polyvest Refractory Die Material available from Whip Mix Corp., Louisville, Ky. and Synvest Refractory Die Material available from Jeneric/Pentron Inc., Wallingford, Conn. Both investments were found adequate. Cores were built up in two applications and fired as given below. The first application was fairly thin. Fired cores were sectioned, polished with 120 and 400 grit sandpaper. Polished cross-sections were studied using an optical microscope at magnifications of 50× and 200×. Cores were found to be fully dense. Only occasionally pores smaller than 30 um were observed. Some of the copings were built up to full crowns using OPC® 3G™ porcelain available from Jeneric/Pentron Inc., Wallingford, Conn. and found to be more than adequate in aesthetics and function. Additionally, the powder of composition 26 was wet-condensed into bars. The bars were fired and polished as per ISO-6872. Three-point bend testing was conducted on ten bars and the flexure strength was measured to be 241±25.

TABLE 6 26 (= 11 from composition 24 25 Table 3) oxide Wt % Mole % Wt % Mole % Wt % Mole % SiO₂ 68.7 64.08 70.6 64.73 68.8 63.68 B₂O₃ — — 0.9 0.71 1.2 1.00 Al₂O₃ 4.8 2.64 4.8 2.59 4.8 2.62 ZnO 0 0.00 0 0.0 0 0.00 MgO 0 0.00 0 0.0 0 0.00 SrO 0 0.00 0 0.0 0 0.00 CaO 1.0 1.0 0.5 0.49 1.0 0.99 BaO 2.8 1.02 1.4 0.50 2.8 1.02 Li₂O 14.4 27.01 14.7 27.10 14.4 26.80 K₂O 2.2 1.31 2.1 1.23 2.2 1.30 Na₂O 1.5 1.36 1.4 1.24 1.4 1.30 ZrO₂ 0 0.00 0 0.00 0 0.00 TiO₂ 0 0.00 0 0.00 0 0.00 P₂O₅ 3.3 1.30 3.6 1.40 3.3 1.29 Tb₄O₇ 0.7 0.05 0 0.00 0 0.00 CeO₂ 0.7 0.23 0 0.00 0 0.00 Molar Ratio of 1.78 1.34 1.76 (Na₂O + K₂O + CaO + SrO + BaO)/(Al₂O₃ + ZnO) Firing 890° C. × 1 min 890° C. × 1 min 890° C. × 1 min Temperature hold hold hold

The glass-ceramics of the present invention have the capability to be used to fabricate dental articles using powder application techniques, pressing techniques or machining techniques to provide single or multi-unit dental restorations at temperatures below about 950° C. using already existing, commercially available equipment such as the Autopress® available from Jeneric/Pentron, Wallingford, Conn. Pressability or ability to flow and be pressed into complex shapes of dental restorations at these temperatures is achieved due to the presence of a sufficient amount of the residual glass in the resulting glass-ceramic, in the range of about 15%-60% by volume. The glass-ceramics of the present invention have the capability to be shaded by admixing pigments to the glass-ceramic powder by methods commonly used for dental porcelains, or alternatively, to the glass batch prior to melting the starting glass composition.

As will be appreciated, the present invention provides a simple and effective method for producing lithium disilicate glass-ceramic compositions and dental restorations therefrom. While various descriptions of the present invention are described above, it should be understood that the various features can be used singly or in any combination thereof. Therefore, this invention is not to be limited to only the specifically preferred embodiments depicted herein.

Further, it should be understood that variations and modifications within the spirit and scope of the invention may occur to those skilled in the art to which the invention pertains. Accordingly, all expedient modifications readily attainable by one versed in the art from the disclosure set forth herein that are within the scope and spirit of the present invention are to be included as further embodiments of the present invention. The scope of the present invention is accordingly defined as set forth in the appended claims. 

What is claimed is:
 1. A method of making a lithium disilicate dental product comprising: melting a starting glass composition at temperatures within the range of about 1200 to about 1600° C.; forming the molten glass into shaped blanks; annealing the glass blanks at temperatures in the range of 300° to about 600° C. for a time in the range of about 15 minutes to about 8 hours; subjecting the glass blanks to one or more heat treatments in the temperature range of from about 400° to about 1100° C. to convert the glass blanks into glass-ceramic blanks.
 2. The method of claim 1 wherein the blanks are in the shape of pellets.
 3. The method of claim 1 wherein the blanks are in the shape of rods.
 4. The method of claim 2 comprising: pressing the blanks into the dental product.
 5. The method of claim 1 wherein crystallization of lithium disilicate is effected in the glass blanks afier annealing when subjected to one or more heat treatments in the temperature range of from about 400° to about 1100° C.
 6. The method of claim 1 wherein subjecting the glass blanks to one or more heat treatments in the temperature range of from about 400° to about 1100° C. comprises a first nucleation step and a second crystal growth step.
 7. The method of claim 6 wherein the first nucleation step comprises heating the glass blanks to a temperature in the range of about 450° to about 700° C.
 8. The method of claim 6 wherein the second crystal growth step comprises heating the nucleated glass in the range of about 800° to about 1000° C.
 9. The method of claim 6 wherein the first nucleation step comprises heating the glass blanks to a temperature in the range of about 500° to about 650° C.
 10. The method of claim 6 wherein the second crystal growth step comprises heating the nucleated glass in the range of about 830° to about 930° C.
 11. The method of claim 6 wherein the first nucleation step comprises about a one hour soak at about 645° C. and wherein the second crystal growth step comprises about a four hour soak at about 850° C.
 12. The method of claim 1 comprising machining the glass-ceramic blanks into the dental product.
 13. The method of claim 4 wherein the dental product is a dental core and is provided with one or more coatings.
 14. The method of claim 13 wherein the one or more coatings is selected from a ceramic, a sintered ceramic, a glass-ceramic, a porcelain, a glass, a glaze, a composite and mixtures thereof.
 15. The method of claim 13 wherein the one or more coatings has a firing temperature in the range of about 700° to about 900° C. and a coefficient of thermal expansion (measured from room temperature to its transition temperature) of within about ±2.0×10⁻⁶/° C. of the dental product (measured at the same temperature range).
 16. The method of claim 4 wherein the dental product is selected from the group consisting of orthodontic appliances, bridges, space maintainers, tooth replacement appliances, splints, crowns, partial crowns, dentures, posts, teeth, jackets, inlays, onlays, facing, veneers, facets, implants, abutments, cylinders, and connectors.
 17. The method of claim 1 wherein the glass-ceramic comprises in weight percent: about 62 to about 85% SiO₂; about 1.5 to about 10% Al₂O₃; about 8 to about 19% Li₂O; about 2.5 to about 7% K₂O; and about 0.5 to about 12% P₂O₅.
 18. The method of claim 17 wherein the glass-ceramic further comprises in weight percent: up to about 4.9% B₂O₃; up to about 1.5% F; up to about 5% ZnO; up to about 7% CaO; up to about 2% MgO; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 5% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₂O₇; up to about 2% Nb₂O₅; up to about 2% Ta₂O₅ ; and wherein the molar ratio of (Na₂O+K₂O+CaO+SrO+BaO)/(A₂O₃+ZnO)≧1.3.
 19. The method of claim 1 wherein the glass-ceramic comprises in weight percent: about 64 to about 70% SiO₂; about 1.5 to about 6 Al₂O₃; about 10 to about 15% Li₂O; about 2.5 to about 5% K₂O; and about 2 to about 7 % P₂O₅.
 20. The method of claim 19 wherein the glass-ceramic further comprises in weight percent: up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 2.7% B₂O₃; up to about 2% ZnO; up to about 0.9% CaO; up to about 2% MgO; up to about 3% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅.
 21. The method of claim 1 wherein the glass-ceramic comprises in weight percent: about 62 to about 85% SiO₂; about 5.1 to about 10 Al₂O₃; about 8 to about 19% Li₂O; and about 0.5 to about 12 % P₂O₅.
 22. The method of claim 21 wherein the glass-ceramic further comprises in weight percent: up to about 7% K₂O; up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 4.9% B₂O₃; up to about 5% ZnO; up to about 7% CaO; up to about 2% MgO; up to about 5% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅.
 23. The method of claim 1 wherein the glass-ceramic comprises in weight percent; about 64 to about 70% SiO₂; about 5.2 to about 9 Al₂O₃; about 10 to about 15% Li₂O; and about 2 to about 7 % P₂O₅.
 24. The method of claim 23 wherein the glass-ceramic further comprises in weight percent; up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 5% K₂O; up to about 2.7% B₂O₃; up to about 2% ZnO; up to about 0.9% CaO; up to about 2% MgO; up to about 3% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅.
 25. The method of claim 1 wherein the glass-ceramic comprises in weight percent: about 64 to about 70% SiO₂; about 1.5 to about 6 Al₂O₃; about 10 to about 15% Li₂O; about 2 to about 7 % P₂O₅; about 2.2 to about 5% K₂O; about 0.5 to about 3% Na₂O; and about 0.5 to about 3% B₂O₃.
 26. The method of claim 25 wherein the glass-ceramic further comprises in weight percent: up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 0.9% CaO; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅.
 27. The method of claim 1 wherein the glass-ceramic comprises in weight percent: about 62 to about 76% SiO₂; about 1.5 to about 10 Al₂O₃; about 8 to about 19% Li₂O; about 0.3 to about 7% P₂O₅; and about 0.5 to about 8% Ta₂O₅.
 28. The method of claim 27 wherein the glass-ceramic further comprises in weight percent: up to about 5% B₂O₃. up to about 5% Na₂O; up to about 7% K₂O; up to about 1.5% F; up to about 5% ZnO; up to about 2% MgO; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 7% CaO; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; and up to about 2% Nb₂O₅.
 29. The method of claim 1 wherein the glass-ceramic comprises in weight percent: about 68.8% SiO₂; about 1.3% B₂O₃; about 4.8% Al₂O₃; about 1.0% CaO; about 2.8% BaO; about 14.4% Li₂O; about 2.2% K₂O; about 1.5% Na₂O; and about 3.3% P₂O₅.
 30. The method of claim 1 wherein the glass-ceramic comprises in weight about 67.2% SiO₂; about 1.2% B₂O₃; about 4.7% Al₂O₃; about 1.0% CaO; about 2.7% BaO; about 14.1% Li₂O; about 2.2 % K₂O; about 1.4% Na₂O; about 3.2% P₂O₅; about 0.4% CeO₂; and about 2% Ta₂O₅.
 31. The method of claim 1 further comprising: batching the starting glass composition prior to melting; and adding additives to the starting glass composition.
 32. The method of claim 1 wherein the additives comprise a color changing metal oxide.
 33. The method of claim 32 wherein the color changing metal oxide comprises CeO₂, Tb₄O₇, MnO₂, V₂O₅, NiO₂, TiO₂, or a mixture thereof.
 34. The method of claim 1 wherein the shaped blanks are formed by: pouring the molten glass into molds to form the blanks; and removing the glass blanks from the molds after the blanks have hardened.
 35. The method of claim 1 wherein the blanks are formed by: drawing glass rods from the molten glass melt; and sectioning the rods into the blanks.
 36. A dental product comprising a glass-ceramic consisting essentially of: about 62 to about 85% SiO₂; about 1.5 to about 10% Al₂O₃; about 8 to about 19% Li₂O; about 2.5 to about 7% K₂O; about 0.5 to about 12 % P₂O₅; up to about 4.9% B₂O₃; up to about 1.5% F; up to about 5% ZnO; up to about 7% CaO; up to about 2% MgO; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 5% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₂O₇; up to about 2% Nb₂O₅; up to about 2% Ta₂O₅; wherein the molar ratio of(Na₂O+K₂O+CaO+SrO+BaO)/(Al₂O₃+ZnO)≧1.3; and wherein the 3-point flexure strength is greater than about 370 MPa.
 37. A dental product comprising a glass-ceramic consisting essentially of: about 64 to about 70% SiO₂; about 1.5 to about 6 Al₂O₃; about 10 to about 15% Li₂O; about 2.5 to about 5% K₂O; about 2 to about 7 % P₂O₅; up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 2.7% B₂O₃; up to about 2% ZnO; up to about 0.9% CaO; up to about 2% MgO; up to about 3% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅; and wherein the 3-point flexure strength is greater than about 370 MPa.
 38. A dental product comprising a glass-ceramic consisting essentially of: about 62 to about 85% SiO₂; about 5.1 to about 10Al₂O₃; about 8 to about 19% Li₂O; about 0.5 to about 12 % P₂O₅. up to about 7% K₂O; up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 4.9% B₂O₃; up to about 5% ZnO; up to about 7% CaO; up to about 2% MgO; up to about 5% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅; and wherein the 3-point flexure strength is greater than about 370 MPa.
 39. A dental product comprising a glass-ceramic consisting essentially of: about 64 to about 70% SiO₂; about 5.2 to about 9 Al₂O₃; about 10 to about 15% Li₂O; about 2 to about 7 % P₂O₅; up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 5% K₂O; up to about 2.7% B₂O₃; up to about 2% ZnO; up to about 0.9% CaO; up to about 2% MgO; up to about 3% Na₂O; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅; and wherein the 3-point flexure strength is greater than about 370 MPa.
 40. A dental product comprising a glass-ceramic consisting essentially of: about 64 to about 70% SiO₂; about 1.5 to about 6 Al₂O₃; about 10 to about 15% Li₂O; about 2 to about 7 % P₂O₅; about 2.2 to about 5% K₂O; about 0.5 to about 3% Na₂O; about 0.5 to about 3% B₂O₃; up to about 1.5% F; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 0.9% CaO; up to about 2% TiO₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇, up to about 2% Nb₂O₅; and up to about 2% Ta₂O₅; and wherein the 3-point flexure strength is greater than about 370 MPa.
 41. A dental product comprising a glass-ceramic consisting of: about 62 to about 76% SiO₂; about 1.5 to about 10 Al₂O₃; about 8 to about 19% Li₂O; about .₃ to about 7% P₂O₅; about .₅ to about 8% Ta₂O₅ ; up to about 5% B₂O₃. up to about 5% Na₂O; up to about 7% K₂O; up to about 1.5% F; up to about 5% ZnO; up to about 2% MgO; up to about 7% BaO; up to about 1% SrO; up to about 5% Cs₂O; up to about 7% CaO; up to about 2% TiQ₂; up to about 3% ZrO₂; up to about 1% SnO₂; up to about 1% Sb₂O₃; up to about 3% Y₂O₃; up to about 1% CeO₂; up to about 1% Eu₂O₃; up to about 1% Tb₄O₇; and up to about 2% Nb₂O₅; and wherein the 3-point flexure strength is greater than about 370 MPa. 